US20220306475A1 - Transfer of nanostructures using crosslinkable copolymer films - Google Patents

Transfer of nanostructures using crosslinkable copolymer films Download PDF

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US20220306475A1
US20220306475A1 US17/209,944 US202117209944A US2022306475A1 US 20220306475 A1 US20220306475 A1 US 20220306475A1 US 202117209944 A US202117209944 A US 202117209944A US 2022306475 A1 US2022306475 A1 US 2022306475A1
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substrate
nanostructures
copolymer
monomers
crosslinkable
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Michael Scott Arnold
Robert Michael Jacobberger
Padma Gopalan
Jonathan H. Dwyer
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Wisconsin Alumni Research Foundation
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Priority to KR1020237033914A priority patent/KR20230159456A/ko
Priority to PCT/US2022/070884 priority patent/WO2022204645A1/fr
Priority to EP22776810.8A priority patent/EP4285392A1/fr
Priority to TW111107731A priority patent/TW202240708A/zh
Publication of US20220306475A1 publication Critical patent/US20220306475A1/en
Assigned to WISCONSIN ALUMNI RESEARCH FOUNDATION reassignment WISCONSIN ALUMNI RESEARCH FOUNDATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOPALAN, PADMA, ARNOLD, MICHAEL, Dwyer, Jonathan, JACOBBERGER, ROBERT
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/06—Graphene nanoribbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • Semiconducting graphene nanoribbons are promising candidates for succeeding and/or complementing silicon (Si) in logic microprocessors and Group III-V compounds in radio frequency devices and for integrating into emerging thin film, optoelectronic, spintronic, and quantum devices because of their large current-carrying capacity, high carrier velocity, bandgap tunability, and outstanding thin-body electrostatic control.
  • Si silicon
  • Group III-V compounds in radio frequency devices
  • quantum devices because of their large current-carrying capacity, high carrier velocity, bandgap tunability, and outstanding thin-body electrostatic control.
  • nanoribbons narrower than 5 nm are desirable, as they can have technologically relevant bandgaps arising from quantum confinement effects.
  • Graphene nanoribbons are high aspect ratio graphene structures comprising single-layer or few-layer graphene. Graphene nanoribbons often need to be transferred from the substrates on which they are formed to a device substrate.
  • poly(methyl methacrylate) (PMMA) is coated over the graphene nanoribbons, followed by the etching and removal of the underlying growth substrate. Once the substrate is removed, a PMMA/graphene nanoribbon membrane remains, which can be fished out of the etching solution and transferred onto a desired substrate, such as a silicon dioxide (SiO 2 )/Si wafer. The residual PMMA is then dissolved using a suitable solvent and thermal treatment. While this method works well for graphene nanoribbons having larger widths, it is not well-suited for the transfer of very narrow nanoribbons.
  • Methers for transferring nanostructures between surfaces using crosslinkable organic copolymers are provided.
  • One embodiment of a method for transferring one or more nanostructures from a first substrate to a second substrate includes the steps of: applying a coating of a crosslinkable copolymer over one or more nanostructures on a surface of the first substrate, wherein the crosslinkable copolymer is polymerized from one or more non-crosslinking monomers and one or more comonomers bearing crosslinkable groups; heating the crosslinkable copolymer to induce crosslinking of the crosslinkable copolymer and to form bonds between the crosslinkable copolymer and the surface of the first substrate; releasing the one or more nanostructures and the crosslinked copolymer from the first substrate; transferring the one or more nanostructures and the crosslinked copolymer onto a surface of the second substrate; and removing the crosslinked copolymer from the one or more nanostructures.
  • FIG. 1 panels (a)-(f), is a schematic diagram of a method for transferring nanostructures from one substrate to another substrate.
  • FIG. 2 shows the structures of various monomers bearing crosslinkable azide groups.
  • FIG. 3A shows a scanning electron microscopy (SEM) image of graphene nanoribbons transferred from a Ge(001) substrate to a SiO 2 substrate using a poly((methyl methacrylate)-(glycidyl methacrylate)) copolymer as a transfer medium.
  • Scale bar is 1 ⁇ m.
  • FIG. 3B shows an SEM image of graphene nanoribbons transferred from a Ge(001) substrate to a SiO 2 substrate using a poly(methyl methacrylate) homopolymer as a transfer medium.
  • Scale bar is 1 ⁇ m.
  • Methods of transferring nanostructures from one substrate to another using a crosslinkable copolymer as a transfer medium are provided. While the methods are particularly useful for transferring graphene nanoribbons from a substrate on which they are grown to a device substrate, the methods can be used to transfer a wide variety of nanostructures between a wide variety of different substrates.
  • FIG. 1 panels (a)-(f).
  • the method begins with one or more nanostructures 102 disposed on a surface of a first substrate 100 ( FIG. 1 , panel (a)).
  • a coating of a crosslinkable copolymer 104 is applied over the one or more nanostructures 102 and the exposed areas of the surface of the first substrate 100 ( FIG. 1 , panel (b)).
  • Crosslinkable copolymer 104 is then heated to induce the crosslinking of the copolymer and bond formation between copolymer 104 and first substrate 100 .
  • First substrate 100 is then removed from nanostructures 102 and copolymer 104 .
  • the bonding of copolymer 104 to first substrate 100 via the heat treatment prior to substrate 100 removal is advantageous because the bonds can prevent the premature delamination of the one or more nanostructures 102 from copolymer 104 during the etching of first substrate 100 .
  • One or more released nanostructures 102 are then transferred onto a surface of a second substrate 108 ( FIG. 1 , panel (e)).
  • the transferred nanostructures may then be annealed to bond the nanostructures to the second substrate.
  • the second substrate may include more than one layer.
  • the substrate may include a thin overlayer 108 supported by a thicker handle substrate 110 .
  • Copolymer 104 is then removed and additional device components can be fabricated on and/or around the one or more transferred nanostructures 102 .
  • a field-effect transistor can be fabricated using a SiO 2 /Si substrate ( 108 / 110 ) by depositing a source electrode 112 and a drain electrode 114 on a semiconducting nanostructure 102 ( FIG. 1 , panel (f)).
  • the term nanostructure refers to a structure having at least one dimension (e.g., height, width, length, thickness, or diameter) that is no greater than 1 ⁇ m. This includes structures having at least one dimension that is no greater than 100 nm further includes structures having at least one dimension that is no greater than 10 nm, and still further includes structures having at least one dimension that is no greater than 1 nm.
  • the nanostructures include structures having at least two dimensions (e.g., length and width) that fall within the above-recited size ranges and structures for which even the largest cross-section dimension falls within the above-recited size ranges.
  • the one or more nanostructures may be composed of a variety of materials including inorganic semiconductors, metals (including metal alloys), and inorganic dielectric materials.
  • Narrow, ultrathin, high-aspect ratio nanostructures are particularly good candidates for transfer using the methods described herein.
  • existing methods for the transfer of narrow, ultrathin, high-aspect ratio nanostructures using PMMA homopolymer as a transfer medium typically have a poor transfer yield.
  • the present methods are able to transfer even dense arrays of many nanostructures, including narrow, ultrathin, high-aspect ratio nanostructures, with transfer yields of, or approaching, 100%.
  • Such arrays may include ten, hundreds, or thousands of nanostructures.
  • Graphene nanostructures such as graphene nanoribbons, are examples of ultrathin, high-aspect ratio nanostructures.
  • Monolayer graphene is a two-dimensional hexagonal network of sp 2 hybridized carbon atoms.
  • Graphene nanoribbons are narrow, elongated strips (or “ribbons”) of monolayer graphene having widths and crystallographic edge structures that provide the ribbons with electronic properties, such as electronic bandgaps, that are absent in continuous two-dimensional films of graphene.
  • Nanoribbons can have aspect ratios of at least 5, at least 10, at least 100, or at least 1000.
  • Graphene nanostructures may comprise monolayer graphene or multilayered graphene.
  • the one or more nanostructures may have a variety of shapes, including hollow cylinders (e.g., nanotubes, including carbon nanotubes), solid cylinders (e.g., nanowires, including metal nanowires), and high aspect ratio thin strips (e.g., nanoribbons, including graphene nanoribbons and hexagonal boron nitride (h-BN) nanoribbons).
  • a nanofilm is a type of nanostructure having the form of a layer of material having a thickness falling within the above-recited size ranges, but lateral dimensions (widths and lengths) that exceed 1 ⁇ m. Nanofilms include monolayer films of graphene and monolayer films of h-BN.
  • First substrate 100 may be a substrate upon which the nanostructures are grown using, for example, chemical vapor deposition (CVD) growth.
  • CVD chemical vapor deposition
  • graphene can be grown on germanium (Ge) substrates via CVD.
  • Other metal substrates upon which graphene can be grown include copper (Cu), ruthenium (Ru), nickel (Ni), palladium (Pd), iridium (Ir), and silicon carbide (SiC).
  • the nanostructures may be grown in the form of nanostructures on the growth substrate (i.e., bottom-up growth) or may be lithographically patterned from a larger film of material that is grown on the growth substrate (i.e., top-down fabrication).
  • first substrate 100 need not be a CVD growth substrate, or even a growth substrate.
  • First substrate 100 may be any substrate on which the nanostructures are disposed that can be selectively removed from the nanostructures during the transfer process.
  • first substrate 100 can be composed of a variety of materials, including inorganic materials, such as metals, semiconductors, and dielectric materials.
  • Crosslinkable copolymer 104 is polymerized from a first monomer that lacks crosslinkable functional groups and a comonomer that introduces a crosslinkable functional group into the copolymer.
  • the crosslinkable copolymer may be a random copolymer.
  • a crosslinkable functional group is a functional group that is available to form crosslinks between copolymer backbone chains after the monomers have been polymerized.
  • crosslinkable functional groups are distinct from polymerizable functional groups, such as the C ⁇ C double bonds of (meth)acrylates, that undergo polymerization reactions to form the backbone of the copolymers.
  • the first monomers that are incorporated into the copolymers do not participate in copolymer crosslinking in transfer methods described herein.
  • the copolymers are polymerized from at least one monomer that is a non-crosslinking monomer, two or more non-crosslinking monomers can be incorporated into the copolymers.
  • Suitable non-crosslinking monomers include methyl methacrylate monomers and/or methyl acrylate monomers (collectively referred to as methyl (meth)acrylate monomers), lactic acid monomers, phthalaldehyde monomers, bisphenol A carbonate monomers, and combinations of two or more thereof.
  • the comomoners are monomers bearing crosslinkable functional groups.
  • the crosslinkable functional groups form crosslinks between copolymer backbone chains and are also able to form bonds between copolymer 104 and first substrate 100 .
  • the bonds may be, for example, covalent bonds and/or ionic bonds.
  • the copolymers are polymerized from at least one monomer bearing a crosslinkable group, two or more crosslinking monomers can be incorporated into the copolymers.
  • Suitable crosslinkable groups include groups that undergo free-radical polymerization processes, such as epoxy groups, vinyl groups, and azide groups. Monomers bearing these groups include azido-substituted methacrylates, acrylates and styrenic monomers.
  • These monomers which are described in Mansfeld, Ulrich, et al. Polymer Chemistry 1.10 (2010): 1560-1598, include those having the structures shown in FIG. 2 . These structures can be expanded to o, p, and m substitution on the benzene ring and to include linkers from 1-12 methylene units in the acrylates and methacrylates.
  • crosslinkable copolymers are polymerized from only one or more of the non-crosslinking monomers listed above and one more of the crosslinkable group-bearing monomers listed above.
  • other non-crosslinking monomers and crosslinkable group-bearing monomers can be used.
  • Copolymers of methyl (meth)acrylate and glycidyl methacrylate and/or glycidyl acrylate are one example of a crosslinkable copolymer that can be used.
  • the copolymers may consist of only polymerized of methyl (meth)acrylate and glycidyl (meth)acrylate monomers.
  • the layer of crosslinkable copolymer 104 is cured to induce crosslinking and substrate-copolymer bond formation.
  • Thermal curing of the copolymer can be carried out by heating the copolymer to a temperature at which the crosslinkable groups undergo crosslinking reactions and copolymer-substrate bond formation.
  • the optimal curing temperature will vary depending upon the particular comonomers and first substrates being used. Temperatures in the range from about 100° C. to about 250° C. are typically sufficient.
  • the crosslinkable copolymers bond more strongly to the first substrate and, as a result, are able to transfer even very narrow nanostructures between substrates with high yields.
  • the crosslinkable comonomers are a minor component in the copolymer; they are present at a concentration sufficient to provide enhanced substrate bonding and polymer rigidity, relative to a PMMA homopolymer.
  • the concentration of polymerized crosslinkable monomers in the copolymers is desirably limited.
  • the comonomers bearing the crosslinkable groups make up no more than 20 mol.
  • the comonomers bearing the crosslinkable groups make up no more than 10 mol. % of the copolymer, no more than 6 mol. % of the copolymer, and no more than 4 mol. % of the copolymer.
  • the polymerized crosslinkable group-bearing comonomer may make up 1 mol. % to 20 mol. % of the copolymer, including embodiments in which the polymerized crosslinkable group-bearing comonomer make up from 2 mol. % to 8 mol. % of the copolymers.
  • the balance of the copolymers is formed from polymerized non-crosslinking monomers.
  • the copolymer layer should be sufficiently thick to facilitate handling during the nanostructure transfer process, but is not otherwise particularly limited. However, unnecessarily thick layers will extend the time needed to remove the copolymer. Generally, a thickness in the range from about 100 nm to 1 ⁇ m is sufficient. If cost or other concerns make it undesirable to use a thick layer of the copolymer, a thin layer of the copolymer can be applied to the nanostructures and a thicker layer of a second homopolymer or copolymer, such as a PMMA homopolymer, can be applied over the copolymer to provide a multilayered polymeric transfer medium.
  • a second homopolymer or copolymer such as a PMMA homopolymer
  • first substrate 100 can be selectively removed using, for example, a wet or dry etch. Suitable etchants will remove first substrate 100 without etching the one or more nanostructures 102 or the copolymer 104 , and, therefore, etchant selection will depend on the particular substrates, nanostructures, and copolymers being used.
  • a H 2 O:HF:H 2 O 2 etch can be used to selectively remove a Ge substrate, and an aqueous solution of iron nitrate or iron chloride can be used to remove a Cu substrate.
  • Second substrate 108 may be composed of various materials, including metals, semiconductors, and dielectric materials. Inorganic and organic (e.g., polymer) substrates can be used. As shown in the embodiment of FIG. 1 , panel (e), second substrate 108 may be a multilayered substrate. For example, a substrate comprising a relatively thin layer 108 , such as a dielectric layer, over a thicker support 110 can be used. Illustrative examples of substrates onto which the nanostructures can be transferred include SiO 2 /Si substrates, polyethylene terephthalate (PET) substrates, sapphire substrates, and mica substrates.
  • PET polyethylene terephthalate
  • the transfer to second substrate 108 can be a wet transfer or a dry transfer.
  • the copolymer 104 /nanostructure 102 /first substrate 100 stack is submerged in wet etchant 106 to selectively remove first substrate 100 .
  • the resulting released copolymer 104 /nanostructure 102 stack can then be transferred to and floated on the surface of a water bath.
  • Second substrate 108 / 110 is then used to lift the copolymer 104 /nanostructure 102 stack out of the water bath.
  • the copolymer 104 /nanostructure 102 /second substrate 108 / 110 stack can then be dried.
  • the copolymer 104 /nanostructure 102 /second substrate 108 / 110 stack can be heated to a temperature that promotes adhesion between one or more nanostructures 102 and the surface of the second substrate 108 .
  • temperatures in the range from about 100° C. to about 150° C. are sufficient.
  • Copolymer 104 is then selectively removed from the one or more nanostructures 102 .
  • the removal of copolymer can be achieved with organic solvents, a thermal anneal, or a combination thereof.
  • the copolymer is first solvated using a suitable solvent and any residual polymer is then removed during the thermal anneal.
  • suitable solvents include acetone and N-methyl-2-pyrrolidone (NMP).
  • NMP N-methyl-2-pyrrolidone
  • Annealing temperatures in the range from 300° C. to 500° C. are typically suitable. However, temperatures outside of this range can be used.
  • This example illustrates a method of transferring an array of graphene nanoribbons from a Ge CVD growth substrate to a SiO 2 /Si device substrate using a PMMA-GMA copolymer as a transfer medium.
  • the transfer process is compared to an analogous transfer process in which a PMMA homopolymer is used as a transfer medium.
  • a degenerately doped Si wafer with 15 nm of thermally grown SiO 2 was chosen as the transfer substrate because it can serve as a universal back-gate for the fabrication of a field-effect transistor (FET), as depicted in panel (f) of FIG. 1 .
  • FET field-effect transistor
  • Graphene nanoribbons were grown via anisotropic CVD growth on a Ge(001) wafer. Methods for growing graphene nanoribbons via anisotropic CVD growth on Ge(001) are known and more details regarding these methods can be found in Way, Austin J., et al., The journal of physical chemistry letters 10.15 (2019): 4266-4272 and Way, Austin J., Robert M, Jacobberger, and Michael S. Arnold, Nano letters 18.2 (2018): 898-906.
  • the graphene nanoribbons were transferred to SiO 2 on Si using a PMMA-GMA copolymer.
  • the copolymer was polymerized from 96 mol % methyl methacrylate (MMA) with 4 mol % of thermally crosslinkable glycidyl methacrylate (GMA), as described in Liu, C. et al., Macromolecules, 2011, 44 (7), 1876-1885.
  • the PMMA-GMA (96% PMMA, 4% GMA) was spin-coated on the graphene nanoribbons and the exposed areas of the Ge(001) surface and then thermally annealed at 160° C.
  • the backside of the sample that was uncoated with polymer underwent an O 2 plasma etch (50 W, 10 mTorr, 10 sccm of O 2 ) for 3 min (Unaxis 790 Reactive Ion Etcher) to remove graphene.
  • the sample was then floated on 3:1:1 H 2 O:HF:H 2 O 2 to etch away the Ge substrate.
  • the released nanoribbon/copolymer membrane was transferred from the Ge etchant to three successive H 2 O baths and finally to a piranha cleaned SiO 2 (15 nm) on Si substrate.
  • the transferred nanoribbon/copolymer membrane and the SiO 2 /Si substrate were then spin dried and then annealed at 120° C.
  • FIG. 3A is an SEM image of the graphene nanoribbon array after the transfer to the SiO 2 showing that the graphene nanoribbons were uniformly transferred with a nearly 100% transfer yield over the 5 ⁇ 5 mm 2 surface area of the SiO 2 substrate.
  • FIG. 3B is an SEM image of the graphene nanoribbon array after the transfer to the SiO 2 showing a poor graphene nanoribbon transfer yield of approximately 25%, with a large section (lower area) of the surface of the SiO 2 substrate having no transferred graphene nanoribbons.

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US17/209,944 US20220306475A1 (en) 2021-03-23 2021-03-23 Transfer of nanostructures using crosslinkable copolymer films
KR1020237033914A KR20230159456A (ko) 2021-03-23 2022-03-01 가교성 코폴리머 필름을 사용한 나노구조체의 전사
PCT/US2022/070884 WO2022204645A1 (fr) 2021-03-23 2022-03-01 Transfert de nanostructures à l'aide de films de copolymère réticulables
EP22776810.8A EP4285392A1 (fr) 2021-03-23 2022-03-01 Transfert de nanostructures à l'aide de films de copolymère réticulables
TW111107731A TW202240708A (zh) 2021-03-23 2022-03-03 使用可交聯共聚物膜轉移奈米結構

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US20070092431A1 (en) * 2005-06-28 2007-04-26 Resasco Daniel E Methods for growing and harvesting carbon nanotubes
US20190232630A1 (en) * 2018-01-27 2019-08-01 Tsinghua University Method for transferring two-dimensional nanomaterials

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AU3397302A (en) * 2000-10-31 2002-05-15 Kimberly Clark Co Heat transfer paper with peelable film and crosslinked coatings
US10106643B2 (en) * 2015-03-31 2018-10-23 3M Innovative Properties Company Dual-cure nanostructure transfer film
CN111128637B (zh) * 2018-11-01 2021-02-26 清华大学 场发射体的制备方法

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Publication number Priority date Publication date Assignee Title
US20070092431A1 (en) * 2005-06-28 2007-04-26 Resasco Daniel E Methods for growing and harvesting carbon nanotubes
US20190232630A1 (en) * 2018-01-27 2019-08-01 Tsinghua University Method for transferring two-dimensional nanomaterials

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